Aromatic nitrogen compounds



Patented Apr. 21, 1953 UNITED STATES ARQMATIC NITROGEN COMPOUNDS Adrien S. Du Bois, Jersey City, N. 3., and Emery I. Valko, New York, N. Y., assignors to Onyx Oil & Chemical Company, Jersey City, N. J... a corporation of Delaware No Drawing. Continuation of application Serial,

No. 564,548, November 21, 1944. This application December 28, 1946, Serial No. 719,139

9 Claims. 1

Our invention relates to novel organic compounds particularly valuable for use as surface active agents. and as germicides. The compounds are characterized in that they contain at least two side groups in para relation on a. benzene nucleus, one of these side groups being an alkyl group containing six to eighteen carbon atoms, the other being a group comprising an alkyl portion terminating in an ionizing, basic nitrogen atom.

This application is a continuation of our application, Serial Number 564,548, filed November 21, 1944, dealing with the production of alkoyl phenyl alkyl halides.

The preferred compounds of our present invention conform to the formulae in which R is an alkyl radical containing six to eighteen carbon atoms, n is an integer greater than 1, X is a halogen atom, most suitably a bromine or chlorine atom, R1, R2 and R3 are hydrogen or monovalent hydrocarbon radicals and in which the circle (Formula. I) indicates that the nitrogen atom is part of a heterocyclic ring system. As exemplary of such compounds may be mentioned: hexyl phenethyl pyridinium bromide, dodecyl phenethyl pyridinium bromide, octyl phenethyl pyridinium bromide, lauryl phenylpropyl quinolinium chloride, undecyl phenylbutyl quinolinium chloride, hexadecyl phenylpropyl picolinium bromide, octadecyl phenethyl isoquinolinium bromide, heptyl phenethyl ammonium chloride, octadecyl phenylpropyl ammonium bromide, undecyl phenylbutyl trimethyl ammonium bromide, hexyl phenethyl dimethyl ammonium chloride, nonyl phenylpropyl benzyl ammonium bromide, the chlorides and bromides of N-hexa phenethyl morpholine, etc.

In addition to compounds meeting the type formula, supra, our invention embraces compounds in which the nitrogen atom forming part of one of the two necessary groups attached to the benzene nucleus has a valency of three.

Although other methods of preparation are possible, We usually prepare. our preferred compounds by one 01 twomethods;

(a) Reduction of compounds of the formulae- Ra. X

in which R, n, etc. have thesame significance as in the preceding formulae.

(b) Reaction of compounds of the formula in which R, 12, etc. have the same significance with ammonia or with amines, such as those indicated by the list of representative compounds above, e, g. pyridine, quinoline, isoquinoline, diethylamine, trimethylamine, benzylamine; morpholine, etc.

We have found that the reduction procedure, which results in the conversion of the carbonyl radical to a methylene radical with the result that the compound becomes more surface active, proceeds with particular advantage when nascent hydrogen produced by contacting metallic zinc, preferably in granulated form, with concentrated aqueous hydrochloric acid is employed as the reducing agent.

The carbonyl-containing compounds subjected to reduction are readily prepared, in accordance with our copending application, Serial No. 719,140, filed December 28, 1946, by reacting the corresponding allgoyl pheny alkyl halide,

VIi

no o Qc Hax produced as by the acylation of the corresponding halogenated-alkyl phenyl compounds described therein in the presence of a Friedel- Crafts catalyst. with an amine. In place of the amine, ammonia may be used, the choice as between ammonia and, amines and as between amines being determined, of course, by the product desired upon the reduction;

The compounds of Formula V used-in method (1)), supra, are advantageously produced according to our copending application, Serial No. 719,138, filed. December 28, 1946, by reduction of the corresponding alkoyl compounds, i. e. compounds meetign Formula. VI.

Compounds, within. the. scope of our invention,

but which do not meehthe time iormulaey first,

given herein, are prepared when compounds of the formula VII in which R, R1, R2, and n have the same significance as heretofore are subjected to'treatment, as with nascent hydrogen, preferably used in the presence of a solvent, ethylene glycol diethyl ether, for example, to convert the carbonyl radical to a methylene radical. Dodecyl phenethyl diethyl amine and hexyl phenethyl diethyl amine are exemplary of compounds we produce by this method.

The following examples are submitted by way of illustrating practices of our invention.

Example I Example II 78 parts by weight of dodecyl phenethyl bromide were mixed with 20 parts by weight of pyridine and the mixture kept at 140 C. for three hours, whereafterit was extracted with petroleum ether. The product was soluble in water. Its killing dilution was 123,000 against Eberthella typhosa at 20 C. Titration for bromine demonstrated that the chemical formula was that of dodecyl phenethyl pyridinium bromide.

Example III 20 parts by weight of octyl phenethyl bromide were mixed with 5 parts by weight of pyridine and the mixture kept at 140 C. for one hour. After extraction with petroleum ether, the titration for bromine demonstrated that the product was octyl phenethyl pyridinium bromide. Its killing dilution was 1:1,600 against Eberthella typhosa at 20 C.

Example IV 6 parts by weight of lauroyl phenethyl diethylamine was treated for six hours with a mixture containing 40 parts by weight of ethyleneglycol diethyl ether, 150 parts concentrated aqueous HCl, and 30 parts by weight of zinc granules. Gaseous HCl was bubbled through the well-agitated reaction mixture for six hours. After this, the reaction mixture was mixed with aqueous caustic soda until it became alkaline and was extracted with ether. Evaporation of the ether yields dodecyl phenethyl diethyl amine;

Example V 4 parts by weight ofcaproyl phenethyl diethyl amine weremixed with 60 parts by weight of ethyl alcohol, 150 parts by weight of concentrated hydrochloric acid and 30'parts by weight of zinc granules. The reaction is carried out as in Example IV. The reaction product is distilled under 4 mm. Hg pressure at 154-157 C. yielding hexyl phenethyl diethyl amine.

We claim: 1. p-Hexyl phenethyl pyridinium bromide. 2. p-Dodecyl phenethyl pyridinium bromide. 3. p-Octyl phenethyl pyridinium bromide 4. Organic chemical compounds conforming to the formula in which R represents an alkyl group containing from 6 to 18 carbon atoms, n represents an integer greater than 1, and R1, R2, and R3 are selected from the group consisting of hydrogen and monovalent hydrocarbon radicals, in which N is linked directly to the terminal carbon atom of the (CHzM group, and in which X represents a halogen atom.

6. Organic chemical compounds conforming to the formula in which R represents an alkyl group containing from 6 to 18 carbon atoms, n is an integer greater than 1 and A is a quaternary ammonium radical of the class consisting of pyridinium, quinolinium, picolinium, isoquinolinium and the morpholinium radicals, the nitrogen of the A radical being linked directly to the terminal carbon of the (CI-I2) group and also to a halogen atom.

7.'The organic chemical compounds of claim 4 in which A is the trimethyl ammonium chloride radical.

8. The organic chemical compounds of claim 4 in which A is the triethyl ammonium chloride radical.

9. A compound represented by the following formula:

where R is an alkyl radical containing at least 7 carbon atoms, n is an integer greater than one. N ERI is a tertiary amine, X is an anion.

ADRIEN S. DU BOIS, EMERY I. VALKO.

I References Cited in the file of this patent UNITED STATES PATENTS 

9. A COMPOUND REPRESENTED BY THE FOLLOWING FORMULA 